CN102741221B - Amino (methyl) acrylate of radiation-hardenable - Google Patents

Amino (methyl) acrylate of radiation-hardenable Download PDF

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Publication number
CN102741221B
CN102741221B CN201180008220.3A CN201180008220A CN102741221B CN 102741221 B CN102741221 B CN 102741221B CN 201180008220 A CN201180008220 A CN 201180008220A CN 102741221 B CN102741221 B CN 102741221B
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methyl
acrylate
amino
amine
radiation
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CN102741221A (en
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X·德吕特雷
T·兰杜克斯
J-Y·萨尔维亚托
L·德魏勒
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Allnex Belgium NV SA
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UCB SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to amino (methyl) acrylate obtained with the mixture reaction of the thinner of (methyl) acroleic acid esterification by amine and carbamate (methyl) acrylate, and manufacture the purposes in coating, tackiness agent, varnish and ink.Amino of the present invention (methyl) acrylate is particularly suitable in the sealing compositions of parquet floor and laminated floor.

Description

Amino (methyl) acrylate of radiation-hardenable
The present invention relates to amino (methyl) acrylate obtained by the addition reaction of (methyl) acrylate and amine, and relate to their purposes in the radiation-hardenable composition being suitable for industrial coating.
Because timber has beauty of nature and the atmosphere of its imparting room warmth, therefore wood floorboards coverture obtains immense success always.Timber or laminated mulching material (flooring) are the application of requirement harshness, and need good wearability.Wearability will depend on core material and coating property.
Radiation-hardenable composition uses for many years in parquet floor and laminates finishing (finishing), and has obtained excellent reputation, because the scratch resistance of its excellence and wearability.UV/EB solidification also allows the production method meeting very much cost benefit and lean.In fact, panel can carry out roller coat by 100% solvent-free solid system, then carries out online UV/EB curing schedule immediately.
Good wear resistance, the tolerance of the abrasive effect of particularly good anti-thin grit such as sand, expects for parquet floor and laminated mulching material very much.Develop special carbamate (methyl) acrylate and be used for this wear resistance, and commercially.
But, still there is the lasting market requirement for allowing carbamate (methyl) acrylate obtaining having the curing activity of raising and the coating of such as excellent sticking power, scratch resistance and wear resistance.To having reactive carbamate (methyl) acrylate adapted with the wood finishing linear velocity of typical approximately 25-30m/min, still there is further demand.
The amination of (methyl) acrylic compound is known.Such as, WO 02/32851 describes DMA(dimethyl amine) amination of alpha, beta-unsaturated esters for being obtained by (methyl) vinylformic acid and alcohol or polyol reaction.Amine/alpha, beta-unsaturated esters adducts can with the blend radiation curing of polymer precursor as carbamate (methyl) acrylate.But, because amine/alpha, beta-unsaturated esters adducts is not containing residual amine, in WO02/32851, there is not the amination of carbamate (methyl) acrylate.
In this context, we provide now and are reacted by least one amine (A) and the mixture (M) that comprises at least one carbamate (methyl) acrylate (B) of 15-99wt% and at least one (methyl) acroleic acid esterification thinner (C) of 1-85wt% and amino (methyl) acrylate that obtains.
In the present invention, term " (methyl) acrylic acid series " be interpreted as not only comprising acrylic compounds but also comprise methacrylic acid based compound or their derivative with and composition thereof.
The compound of " (methyl) acroleic acid esterification " more particularly refers to the compound comprising at least one acrylate (CH2=CHCOO-) group and/or at least one methacrylic ester (CH2=CCH3COO-) group.When acrylate group and methacrylate based group all exist, they may reside on identical or different compounds.
Amine (A) for the preparation of amino of the present invention (methyl) acrylate can be selected from uncle and/or secondary amine.Amine (A) for the preparation of amino of the present invention (methyl) acrylate is usually selected from and comprises at least one primary amino group-NH 2primary amine (A1) and/or be selected from the secondary amine (A2) comprising at least two parahelium group-NH.Such secondary amine (A2) is used to have the advantage allowing chain extension.The reaction that the compound (B) that " chain extension " means at least two (methyl) acrylic compound (B) or at least two (methyl) acrylic compound (C) or at least one (methyl) acroleic acid esterification is connected by the intermediate of amine (A2) with at least one (methyl) acrylic compound (C).But, usually preferably use and comprise at least one primary amino group-NH 2primary amine (A1).
The weight-average molecular weight (MW) of the primary amine (A1) that the present invention uses is preferably 31 to 300 dalton, more preferably 45 to 250 dalton.In the present invention, molecular weight is generally calculated by the chemical formula of amine (A1).
Suitable amine (A1) is corresponding to formula R 1-NH 2(I), wherein R 1represent alkyl, optionally replaced by hydroxyl, alkoxyl group, tertiary amine and/or aryl.
Amine (A1) such as can be selected from following one or more: methylamine, ethamine, Tri N-Propyl Amine, Isopropylamine, n-Butyl Amine 99, isobutylamine, sec-butylamine, TERTIARY BUTYL AMINE, 3-methyl butyl amine, normal hexyl Amine, n-octyl amine, n-dodecane amine, 2-DEHA, different nonyl amine, cyclopentamine, hexahydroaniline, 2-methylcyclohexyl amine, benzene methanamine, 2-(2-amino ethoxy) ethanol, 5-aminopentanol, thanomin, 3-amino-1-propyl alcohol, α-amino isopropyl alcohol, 2-amino-2-methyl-1-propanol, 3-(diethylamino) propylamine, N, N-dimethylamino neo-pentyl amine, 2-(diethylamino) ethylamine, 1-methyl-4-(diethylamino) butylamine, 2,2-(di-t-butyl is amino) ethylamine, 3-(dimethylamino) propyl group amine, 2-methoxy ethyl amine, 2-ethoxyethyl group amine, 3 methoxypropyl amine, 1-methoxyl group Isopropylamine, 3-ethoxycarbonyl propyl amine, 3-isopropoxide propyl amine, 3-(2-methoxy ethoxy) propyl group amine, 3-(2-ethyl hexyl oxy) propyl group amine, furfuryl group amine and composition thereof.
Preferred alkylamine (A1), wherein alkyl comprises 1 to 30 carbon atom, particularly 1 to 18 carbon atom, more particularly 1 to 14 carbon atom, and it is optionally optionally substituted with one or more hydroxyl replacement.
Term used herein " alkyl " is defined as the saturated univalence hydrocarbyl comprising and have straight chain, side chain or circular part or its combination.
Particularly preferably be Tri N-Propyl Amine, n-Butyl Amine 99, normal hexyl Amine, 2-DEHA, hexahydroaniline, n-octyl amine, n-dodecane amine, 2-(2-amino ethoxy) ethanol, 5-aminopentanol, thanomin, 3-amino-1-propyl alcohol, α-amino isopropyl alcohol, 2-amino-2-methyl-1-propanol and composition thereof.Especially preferred is thanomin, α-amino isopropyl alcohol, 2-amino-2-methyl-1-propanol and composition thereof.Most preferred ethanol amine, particularly monoethanolamine.
For suitable secondary amine (A2) corresponding R of the present invention 2hN-R 4-NHR 3(II), wherein R 2and R 3represent alkyl independently of one another, it is optionally replaced by hydroxyl, alkoxyl group, tertiary amine and/or aryl, and prerequisite is R 2and R 3can connect to form ring, and R 4be selected from alkylidene group and sub-aralkyl, it comprises and is up to 50 carbon atoms (being typically up to 20 carbon atoms), and can contain 1 to 20 ether bridge (ether bridges) (typically 1 to 8 ether bridge) and/or 1 to 3 tertiary amine bridge (tertiary amine bridges).Term used herein " alkylidene group " means the alkyl of the straight chain of divalence, side chain or ring-type.Term used herein " sub-aralkyl " means the alkylidene group that wherein one or more hydrogen bases are replaced by aryl.
Preferably, R 4be selected from following divalent group: ethylidene, propylene, trimethylene, hexa-methylene, 2,2-dimethylpropylidene, 1-methyl trimethylene, 1,2,3-trimethylammonium tetramethylene, 2-methyl-pentamethylene, 2,2,4-(or 2,4,4-) tri-methyl hexamethylene, between xylylene (metaxylylene), 3,5,5-trimethylammonium sub-hexamethylene-1-base-3-methylene radical, two (sub-hexamethylene-4-base) methane, two (4-methyl sub-hexamethylene-3-base) methane, sub-hexamethylene-1,3-base, sub-hexamethylene-Isosorbide-5-Nitrae-Ji, Isosorbide-5-Nitrae-bis-(sub-third oxygen-3-base) butane, two (trimethylene) methylamine of N, N-, 3,6-dioxa is octylene, the sub-dodecyl of 3,8-dioxa, the sub-tridecyl of 4,7,10-trioxa, poly-(oxygen base tetramethylene), have poly-(the oxygen propylidene) of 2 to 15 1,2-oxypropylene units, have poly-(the oxygen propylidene-altogether-oxygen ethylidene) of 2 to 15 oxypropylene units and 2 to 15 oxyethylene units, 2,2-dimethylpropylidene.
Preferred cyclic secondary amine is diaza-pentamethylene, amylene, hexane, hexene, heptane and heptene.Particularly preferred secondary amine (A2) is 2-methylpiperazine, two uncle (tertio) butyl ethane diamine (also referred to as N, N '-dual-tert-butyl ethane diamine) and composition thereof.
The thinner (C) of (methyl) acroleic acid esterification in the present invention mean carbamate (methyl) acrylate (B) wherein solvable or can be miscible with it the compound of (methyl) acroleic acid esterification.
Preferably the thinner (C) of (methyl) acroleic acid esterification is at room temperature for liquid or the viscosity 25 DEG C time are 1 to 2000mPa.s, are especially those of 1 to 200mPa.s.Measure viscosity according to method described below in the present invention.
Example for (methyl) of the present invention acroleic acid esterification thinner (C) is propenoic acid beta-carboxyl ethyl ester, (methyl) butyl acrylate, (methyl) methyl acrylate, (methyl) i-butyl base ester, (methyl) 2-ethylhexyl acrylate, (methyl) cyclohexyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) isobornyl acrylate, (methyl) isooctyl acrylate ester, the positive Lauryl Ester of (methyl) vinylformic acid, (methyl) vinylformic acid octyl group/decyl ester, (methyl) HEA, Phenoxyethyl (methyl) acrylate, nonyl phenol ethoxylate list (methyl) acrylate, 2-(-2-ethoxy ethoxy) ethyl (methyl) acrylate, 2-butoxyethyl group (methyl) acrylate, NVP, 1,6 hexanediol diacrylate (HDDA), pentaerythritol triacrylate (PETIA), Viscoat 295 (TMPTA), propylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), phenyl glycidyl ether acrylate, (methyl) acrylate of uncle-capric acid glycidyl esters, and its possible (methyl) acroleic acid esterification ethoxylation and/or propenoxylated derivative (such as (methyl) acroleic acid esterification ethoxylation and/or propenoxylated TriMethylolPropane(TMP), glycerine, dimethyltrimethylene glycol and/or tetramethylolmethane, the ethoxylation of Phenoxyethyl (methyl) acrylate and/or propenoxylated derivative etc.).
The thinner (C) of (methyl) acroleic acid esterification used in the present invention can be selected from one or more single (methyl) acrylate, one or more two (methyl) acrylate and/or one or more three (methyl) acrylate.They are preferably selected from one or more single (methyl) acrylate and/or one or more two (methyl) acrylate.Preferably, the thinner of these (methyl) acroleic acid esterifications does not comprise any beta-hydroxy.
Particularly preferably two (methyl) acrylate.
(methyl) acrylate of usual use polyvalent alcohol, particularly dibasic alcohol.
What be applicable to is such as 1,6-hexylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, propenoxylated glycerine three (methyl) acrylate and composition thereof.It is particularly suitable that 1,6-hexylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate and composition thereof.Their acrylate is most preferred.
Carbamate (methyl) acrylate is known in the art and is the product of commercially available acquisition.Carbamate (methyl) acrylate (B) in the present invention means the carbamate groups and at least one compound corresponding to (methyl) acrylate group of formula IV that correspond to formula III containing at least one, and in structural formula (IV), R is hydrogen atom or methyl.
formula III
formula IV
To be preferably used for carbamate of the present invention (methyl) acrylate (B) be elongation at break is flexible amino manthanoate (methyl) acrylate of 10-500%, more preferably 50-300%.According to ASTM D 638, by the stretching test measurement elongation at break of the thin free film of the radiation curing of carbamate (methyl) acrylate.
Can be aliphatic carbamate (methyl) acrylate or aromatic urethanes (methyl) acrylate for carbamate of the present invention (methyl) acrylate (B).
The example of suitable carbamate (methyl) acrylate (B) comprise business-like those, name is called 204, 205, 210, 230, 270 etc.
Preferably, comprise at least two (methyl) acrylate groups for carbamate of the present invention (methyl) acrylate (B), and preferably six at the most, more preferably four (methyl) acrylate groups at the most.
Two or three (methyl) acrylate groups are preferably comprised, more particularly two or three acrylate groups for carbamate of the present invention (methyl) acrylate (B).Specially suitable is carbamate two (methyl) acrylate, even more preferably polyurethane diacrylate.
For carbamate of the present invention (methyl) acrylate (B) typically via
(a) at least one polyisocyanates,
(b) at least one hydroxyl (methyl) acrylate, and
(c) optionally, at least one polyvalent alcohol
Reaction and obtain.
Polyvalent alcohol for the preparation of carbamate (methyl) acrylate (B) is selected from polyester polyol, acrylic polyol, polyether glycol, polyolefin polyhydric alcohol, polycarbonate polyol and/or its mixture." polyvalent alcohol " is meant to comprise at least two hydroxyls and has the alcohol of at least 400 daltonian weight-average molecular weight (Mw) measured by GPC herein.Gpc measurement carries out according to method described below in the context of the present invention.Preferred polyvalent alcohol be there are 2 to 4 hydroxyls and Mw be 500 to 5000 daltonian those.The Mw of polyvalent alcohol preferably more than 3000, preferably more than 1000.Particularly preferably glycol, such as polypropylene glycol.
Polyisocyanates for the preparation of carbamate (methyl) acrylate (B) can be comprise at least two isocyanate functional groups and preferably six isocyanate functional groups, the more preferably aromatics of four isocyanate functional groups, cyclic aliphatic and/or aliphatic polyisocyanates at the most at the most.Preferably vulcabond, such as hexa-methylene-vulcabond (HMDI), isophorone-diisocyanate (IPDI), two (4-isocyanato cyclohexyl) methane, toluene diisocyanate (TDI), ditan-4,4 '-vulcabond or ditan-2,4 '-vulcabond (MDI), trimethyl hexamethylene diisocyanate, tetramethyl--m xylene diisocyanate; They two-, three-or the oligopolymer (diphenylmethanediisocyanate be such as polymerized mR L or commodity are called the isomer mixture of the diphenylmethanediisocyanate (MDI) of 2, the 4 ' isomer containing high per-cent of ML); And/or the adducts of they and polyvalent alcohol.
Optionally, the biuret of the isocyanate-functional of the isocyanic ester listed, allophanate class (allophonates), urea diketone and isocyanuric acid ester can be used.Preferred isophorone-diisocyanate, two (4-isocyanato cyclohexyl) methane and toluene diisocyanate.Most preferably two (4-isocyanato cyclohexyl) methane and toluene diisocyanate.
Hydroxyl (methyl) acrylic compound means the compound containing at least one hydroxyl and at least one (methyl) acrylate group.For (methyl) acrylate that suitable compound of the present invention is the polyvalent alcohol of straight chain or branching, wherein at least one hydroxy functional group keeps free, as having (methyl) acrylic acid hydroxy alkyl ester of 1 to 20 carbon atom in alkyl chain.Preferably there is (methyl) vinylformic acid monohydroxy alkyl ester of 1 to 20 carbon atom in alkyl chain.The example of suitable compound comprises (methyl) vinylformic acid methylol ester, (methyl) hydroxyethyl acrylate, (methyl) hydroxyethyl methacrylate, (methyl) hydroxybutyl acrylate, glycerine two (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, ditrimethylolpropane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, caprolactone-hydroxyethyl acrylate adducts and their (gathering) ethoxylation and/or (gathering) propoxylation Equivalent, and composition thereof.Preferred acrylate.Specially suitable is hydroxyethyl acrylate and/or hydroxyethyl methacrylate.
Mixture for reacting with amine (A) in the present invention comprises the thinner (C) of at least one carbamate (methyl) acrylate (B) of 15-99wt% and at least one (methyl) acroleic acid esterification of 1-85wt%.Typically, the content of carbamate (methyl) acrylate (B) is at least 25wt% in the mixture, usually at least 30wt%.Typically, the content of the thinner (C) of (methyl) acroleic acid esterification is 75wt% at the most in the mixture, usually 70wt% at the most.
Mixture for reacting with amine (A) in the present invention preferably comprises the thinner (C) of at least one carbamate (methyl) acrylate (B) of 30-99wt% and at least one (methyl) acroleic acid esterification of 1-70wt%.Here weight percent is the total weight relative to mixture (M) for the preparation of amino of the present invention (methyl) acrylate.
Typically, in mixture (M), carbamate (methyl) acrylate (B) adds up to 100% with the weight percent of the thinner (C) of (methyl) acroleic acid esterification.In the present invention, typically except compound (A), (B) and (C), other reagent is not used to prepare amino of the present invention (methyl) acrylate.
(methyl) reaction between acrylate and amine is known as Michael addition reaction.It is undertaken by the addition of amine on the carbon-carbon double bond of (methyl) acrylate.The reaction of carbamate (methyl) between acrylate and amine can be carried out in case not having catalyzer or solvent to deposit.This reaction can be carried out at the temperature between-30 to 150 DEG C, preferably 25 to 100 DEG C.Although solvent is also nonessential, it can be used for promoting heat and mass.
According to amino of the present invention (methyl) acrylate normally by amine (A) with comprise at least one carbamate (methyl) acrylate (B) and at least one (methyl) acroleic acid esterification thinner (C) mixture reaction and obtain, wherein amine (A) consumption for the equivalence ratio of (methyl) acrylic acid series double bond making the amino-N-H from amine (A) and the thinner (C) by carbamate (methyl) acrylate (B) and (methyl) acroleic acid esterification and provide be 0.01 to 0.9.Therefore, when using primary amine (A1), the quantity of-N-H group is calculated as the-NH provided by this primary amine 2the twice of group.Preferably, the quantity of amine (A) is at least 0.05 for making the amino-N-H of (A) with the equivalence ratio of (methyl) acrylic acid series double bond provided by (B) and (C), and more preferably at least 0.1.This equivalence ratio preferably more than 0.8, more preferably no more than 0.7.This equivalence ratio is no more than 0.5, can be useful more preferably no more than 0.3.
Do not wish the constraint being subject to any mechanism, think and use amine (A1) and (A2) to allow to obtain amino (methyl) acrylate in stoichiometric range according to the present invention, its by chain extension to the degree making them have the feature of optimum balance between acceptable viscosity and good rub.
The invention still further relates to the method for the preparation of amino described herein (methyl) acrylate, wherein at least one amine (A) and the mixture reaction of thinner (C) comprising at least one carbamate (methyl) acrylate (B) as above of 15-99wt% and at least one (methyl) acroleic acid esterification of 1-85wt%.Typically, the content of carbamate (methyl) acrylate (B) is at least 25wt% in the mixture, usually at least 30wt%.Typically, the content of the thinner (C) of (methyl) acroleic acid esterification is 75wt% at the most in the mixture, usually 70wt% at the most.
Preferably, the thinner (C) of at least one carbamate (methyl) acrylate (B) of 30-99wt% and at least one (methyl) acroleic acid esterification of 1-70wt% is comprised for the preparation of the mixture of amino (methyl) acrylate according to the present invention.Here weight percent is the total weight relative to mixture (M) for the preparation of amino of the present invention (methyl) acrylate.
Typically, in mixture, carbamate (methyl) acrylate (B) adds up to 100% with the weight percent sum of the thinner (C) of (methyl) acroleic acid esterification.In the present invention, except compound (A), (B) and (C), other reagent is not typically used to prepare amino of the present invention (methyl) acrylate.
Usually obtain the mixture of different amino (methyl) acrylate, optionally there is compound (B) and/or (C) of remaining (unreacted) (methyl) acroleic acid esterification.
Completing of reaction can be followed the tracks of by the amount such as measuring unhindered amina--see the such as following method provided.When having reacted, can using amino (methyl) acrylate as residuum Product recycling; But, can be reclaimed by conventional distillation and fractionating step in some cases.Preferably, the resistates of unhindered amina is removed from this amino (methyl) acrylate to lower than 1000ppm, more preferably less than 500ppm, most preferably lower than the level of 400ppm.Method by any appropriate removes unhindered amina, such as, carries out air lift at reduced pressure conditions with such as air or nitrogen.Although compound (B) and/or (C) of unreacted (methyl) acroleic acid esterification can be separated from amino (methyl) acrylate, before being further used for radiation-hardenable composition, from this amino (methyl) acrylate, be not usually separated compound (B) and/or (C) of (methyl) acroleic acid esterification.
In order to prevent occurring the effect of (methyl) acrylic ester polymerization in advance, also during reaction or after reaction various inhibitor or stablizer can be added.Typical inhibitor such as aromatic series or aliphatic phosphorous acid ester can be used.
Amino of the present invention (methyl) acrylate preferably has the viscosity of 100 to 50000mPa.s 25 DEG C time.Preferably 25 DEG C time, viscosity is at most 20000mPa.s.More preferably 25 DEG C time viscosity be at least 2000mPa.s.
Amino of the present invention (methyl) acrylate preferably has the nitrogen content of at least 0.1wt%, more preferably at least 1.0wt%.This nitrogen content preferably more than 5.0wt%, more preferably no more than 3.5wt%.Numerical value given here is theoretical value, from amine with wherein calculate for the preparation of the content of amino of the present invention (methyl) acrylate.The invention still further relates to the purposes of this amino (methyl) acrylate, the purposes especially in radiation-hardenable composition described below.
Have been found that amino as described in the present invention (methyl) acrylate is very effective in UV/EB solidification, and can be used alone or use together with the compound of other (methyl) acroleic acid esterification.This amino (methyl) acrylate is easily solidified by ultraviolet radiation or electron beam irradiation.
Good reactivity is shown under being exposed to radiation according to amino of the present invention (methyl) acrylate.
Allow to obtain to have excellent abrasive resistance and scrath resistance according to amino of the present invention (methyl) acrylate and advantageously also have good reactive coating.What adopt coating composition according to the present invention to obtain is being exposed to the radiation (situation of UV light: press mercury H bulb in 2,120w/cm) the reactivity of period, typically between 20 to 45m/min, more particularly between 25 to 35m/min, i.e. the typical rate of the state of the art production line.
The coating of the wear resistance obtaining having increase is even allowed according to amino of the present invention (methyl) acrylate.Advantageously, further feature as chemically-resistant and thermotolerance, sticking power and hardness, snappiness etc. be not subject to rub increase negative impact.
Advantageously, allow according to amino of the present invention (methyl) acrylate the coating obtaining the optimum balance be characterised in that between acceptable viscosity and good rub.
Find under impose conditions (UV-Vitalux 300W lamp, 72 hours) according to the yellow trend of amino of the present invention (methyl) acrylate with there is no amination and obtained identical resin-phase is even slightly better than similar.
Useful especially according to amino of the present invention (methyl) acrylate for preparing for wood coating, especially for preparing the sealing compositions of wood floorboards coverture, particularly parquet floor and laminated floor.When using according to radiation-hardenable composition of the present invention, prove that inter coat glues adhesivity excellence.Amino of the present invention (methyl) acrylate is also suitable for the mulching material such as elastic ground coverture of other type.
Can be used for according to amino of the present invention (methyl) acrylate comprising as unique radiation curable compounds in the radiation-hardenable composition of usual composition, or use together with the compound of other radiation curable compounds, particularly (methyl) acroleic acid esterification.
The present invention relates to and comprise the radiation-hardenable composition of at least one according to amino of the present invention (methyl) acrylate.
The present invention be more particularly directed at least one containing at least 5wt% according to the radiation-hardenable composition of amino of the present invention (methyl) acrylate.Preferably, said composition comprises described amino (methyl) acrylate of at least 10wt%.The content of this amino (methyl) acrylate is no more than 99wt% usually.Here weight percent is the total weight relative to radiation-hardenable composition.
Except amino (methyl) acrylate, this radiation-hardenable composition can containing at least one radiation-curable polymer precursor being different from amino described herein (methyl) acrylate.Term " polymer " precursor " for representing monomer or oligopolymer or its mixture, it has suitable polymerizable functional group, preferably comprises one or more (methyl) acrylate or vinyl groups at this chain end or along chain side.This radiation-curable polymer precursor is generally the monomer or oligopolymer that comprise one or more (methyl) acrylate or vinyl groups.Preferably, this radiation-curable polymer precursor is the oligopolymer of (methyl) acroleic acid esterification and/or the monomer of (methyl) acroleic acid esterification.
Such as can comprise the thinner (D) of at least one (methyl) acroleic acid esterification further according to radiation-hardenable composition of the present invention, it can be identical or different from the thinner (C) of (methyl) described above acroleic acid esterification." thinner (D) of (methyl) acroleic acid esterification " in the present invention mean carbamate of the present invention (methyl) acrylate wherein solvable or can be miscible with it the compound of (methyl) acroleic acid esterification.Be somebody's turn to do thinner (D) the lower molecular weight reactive diluent typically of (methyl) acroleic acid esterification.These lower molecular weight reactive diluents typically have 1000 daltonian weight-average molecular weight at the most.In this application, the molecular weight of this thinner is typically calculated by the chemical formula of thinner.
The example of the thinner (D) of such lower molecular weight (methyl) acroleic acid esterification comprises (methyl) vinylformic acid, propenoic acid beta-carboxyl ethyl ester, (methyl) butyl acrylate, (methyl) methyl acrylate, (methyl) i-butyl base ester, (methyl) 2-ethylhexyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid n-hexyl ester, (methyl) isobornyl acrylate, (methyl) isooctyl acrylate ester, the positive Lauryl Ester of (methyl) vinylformic acid, (methyl) vinylformic acid octyl group/decyl ester, (methyl) HEA, Phenoxyethyl (methyl) acrylate, nonyl phenol ethoxylate list (methyl) acrylate, 2-(-2-ethoxy ethoxy) ethyl (methyl) acrylate, 2-butoxyethyl group (methyl) acrylate, (methyl) acrylate of uncle-capric acid glycidyl esters, NVP, 1,6 hexanediol diacrylate (HDDA), pentaerythritol triacrylate (PETIA), Viscoat 295 (TMPTA), phenyl glycidyl ether acrylate, propylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), and the ethoxylation of its (methyl) acroleic acid esterification or/and propenoxylated derivative (ethoxylation of such as (methyl) acroleic acid esterification is or/and propenoxylated TriMethylolPropane(TMP), glycerol, neopentyl glycol and/or tetramethylolmethane, the ethoxylation of Phenoxyethyl (methyl) acrylate and/or propenoxylated derivative etc.).
If used in the present invention, the thinner (D) of (methyl) acroleic acid esterification is preferably selected from one or more single (methyl) acrylate and/or is selected from one or more two (methyl) acrylate.Preferably the thinner of these (methyl) acroleic acid esterifications does not comprise any beta-hydroxy.
According to an embodiment of the invention, the thinner (D) of optional (methyl) acroleic acid esterification is selected from one or more single (methyl) acrylate, and is optionally selected from one or more two (methyl) acrylate.Example that is suitable and preferred two (methyl) acrylate is as provided above.Based on list (methyl) acroleic acid esterification with the thinner (D) of two (methyl) acroleic acid esterification, the content of the thinner (D) of single (methyl) acroleic acid esterification is preferably at least 20wt%, more preferably at least 35wt%, even more preferably at least 50wt%, most preferably at least 80wt%.
In special embodiment according to the present invention, the thinner (D) of optional (methyl) acroleic acid esterification is selected from one or more single (methyl) acrylate.
Example for suitable list (methyl) acrylate (D) of the present invention comprises (methyl) vinylformic acid octyl group/decyl ester, Phenoxyethyl (methyl) acrylate, nonyl phenol ethoxylate list (methyl) acrylate, 2-(-2-ethoxy ethoxy) ethyl (methyl) acrylate, (methyl) acrylate of uncle-capric acid glycidyl esters, the ethoxylation of Phenoxyethyl (methyl) acrylate and/or propenoxylated derivative, and these mixture any.Preferably do not comprise those of any beta-hydroxy.
Particularly preferably be the ethoxylation of Phenoxyethyl (methyl) acrylate and/or propenoxylated derivative, more particularly the ethoxylated derivative of Phenoxyethyl (methyl) acrylate.The most preferably Phenoxyethyl mono acrylic ester (EPEA) of ethoxylation.
Thinner (D) for preferred (methyl) acroleic acid esterification of the present invention is at room temperature for liquid or the viscosity 25 DEG C time are 1 to 2000mPa.s, are especially those of 1 to 200mPa.s.
When deployed, the quantity of thinner (D) in radiation-hardenable composition according to the present invention of (methyl) acroleic acid esterification is generally at least 2wt%, preferably at least 5wt%, more preferably at least 10wt%.The quantity of the thinner (D) of (methyl) acroleic acid esterification is no more than 40wt%, usually preferably more than 15wt%.Here weight percent is relative to the total weight of radiation-hardenable composition.
In yet another embodiment of the present invention, the thinner (D) of any (methyl) acroleic acid esterification is not comprised according to radiation-hardenable composition of the present invention.
Alternately, or except the thinner (D) of above-mentioned (methyl) acroleic acid esterification optionally, radiation-hardenable composition of the present invention can also comprise one or more oligopolymer.Preferred oligopolymer comprises such as hyperbranched polyester polyol (methyl) acrylate of the acrylic oligomers of (methyl) acroleic acid esterification, aromatic acid (methyl) acrylate, the polyhutadiene of (methyl) acroleic acid esterification, the polyester of (methyl) acroleic acid esterification, carbamate (methyl) acrylate, epoxy group(ing) (methyl) acrylate and hyperbranched (methyl) acrylate.
Preferred oligopolymer be weight-average molecular weight be at least 1000 and not higher than 6000 daltonian those, as measured by GPC---vide infra method used.
When deployed, the quantity of oligopolymer in radiation-hardenable composition according to the present invention is generally at least 5wt%, preferred at least 10wt%.The quantity of oligopolymer is no more than 50wt%, usually preferably more than 40wt%.Here weight percent is relative to the total weight of radiation-hardenable composition.
Usually comprise at least one light trigger for this radiation-hardenable composition in the present invention, namely produce the compound of free radical by absorb light, typically UV light.Generally speaking, light trigger content is in the composition between 0 to 15wt%, preferably between 0.01 to 8wt%.Here weight percent is relative to the total weight of radiation-hardenable composition.
Or the radiation-hardenable composition not containing light trigger can pass through electrocuring usually.
The additive that this radiation-hardenable composition also can be commonly used containing this area, such as substrate wetting agents, anti-whipping agent, dispersion agent, flow ability modifying agent, antiseize paste, plasticising thinner, fire retardant, uv-protector, adhesion promoter, antioxidant, toughener and stablizer.The total amount of typical additives is no more than 10wt% usually.Preferably, said composition comprises the above-mentioned typical additives of 0.01 to 5wt%.Here weight percent is relative to the total weight of radiation-hardenable composition.
When needed, this radiation-hardenable composition also can contain one or more pigment or tinting material.The tinting material of composition used in the present invention and pigment can be any pigment known in the art or tinting material.The inventory of suitable pigment can be found in " Colour Index (Color Index) ".More specifically; those pigment can be described as such as Process Yellow 13 (Diarylide Yellow-Irgalite BAW of Ciba; Permanent GR ofClariant); Process Magenta Pigment 57 (Bona Calcium-Ilobona4BY of Sun; Irgalite SMA of Ciba); Process Blue 15.3 (CuPc-Irgalite GLO of Ciba; Hostaperm Blue B2G of Clariant), ProcessBlack 7 (oxidized black-Special Black 250; Special Black 350 ofDegussa) etc.Described tinting material and/or pigment optimization use with the 0-50wt% of this radiation-hardenable composition gross weight, more preferably 0-40wt%.
This radiation-hardenable composition also can comprise the filler of 0 to 20wt% or non-reactive diluent or solvent.The inert plastic of 0 to 20wt% can also be used in radiation-hardenable composition.Inert plastic is the resin of the polyreaction not participating in radiation or EB initiation.The example of this type of inert plastic typically comprises hydrocarbon (hydrocarbon resin of such as styrene-based), acrylic resin (such as acrylic acid series (being total to) polymkeric substance), (gathering) carbamate resins, plastic of poly vinyl acetate resin, polyvinyl chloride (PVC) RESINS, chlorinated polyolefin resin and/or ketone resin.
Its selected composition mixing is prepared by the currently known methods of routine by this radiation-hardenable composition.If needed, can to the heating of this blend to promote mixing.
Radiation-hardenable composition of the present invention can be used in manufacturing coating, particularly industrial coating, tackiness agent, ink and varnish.Ink means liquid ink and sticks with paste ink.
Therefore, the present invention relates to amino (methyl) acrylate or radiation-hardenable composition according to the present invention in the purposes being suitable for preparing in the radiation-hardenable composition of coating, tackiness agent, ink or varnish.
One aspect of the present invention relates to by amino (methyl) acrylate according to the present invention or coating, tackiness agent, ink or the varnish prepared by radiation-hardenable composition according to the present invention.
The invention still further relates to amino (methyl) acrylate or radiation-hardenable composition according to the present invention is being suitable for the purposes in the radiation-hardenable composition on timber (vegetarian noodles (plain) or facing).
The invention still further relates to amino (methyl) acrylate or the purposes of radiation-hardenable composition according to the present invention in the radiation-hardenable composition being suitable for mulching material, more especially wood floorboards coverture (vegetarian noodles or facing).
Radiation-hardenable composition of the present invention is particularly suitable for mulching material application.Such as can apply and comprise wood floorboards coverture (such as parquet floor and laminated floor) and elastic ground coverture according to the mulching material of radiation-hardenable composition of the present invention.Elastic ground coverture can be made up of Vinylite, polyolefine, malthoid, rubber or cork.
Radiation-hardenable composition of the present invention is particularly suitable for manufacturing sealing compositions, and sealing composition is used for this type of mulching material, particularly wood floorboards coverture and more particularly parquet floor and laminated floor.
The invention still further relates to the method for coating mulching material, more particularly wood floorboards coverture (such as parquet floor and laminated floor), the method comprises and applies one deck or multilayer according to radiation-hardenable composition of the present invention to floor base material, and the composition solidification that will apply by being exposed to radiation (such as photochemical radiation, UV optical, electrical from radiation and/or electron beam).
When sealing compositions as timber (such as timber floor), coating composition of the present invention does not preferably comprise the Clear coating of pigment and/or tinting material.Coating composition protection natural timber (vegetarian noodles or facing) of the present invention exempts from stains and wearing and tearing.Clear coating can strengthen wood color and structure.
Wood coating is typically made up of different layers, and every layer has special performance.The sealing agent of typical system comprises (or consisting of) priming paint, one or more layers (optimum selecting three-layer) and top coat subsequently.For the optimum performance of total coating system, expect very much excellent inter coat adhesive power.
Correspondingly, in the method according to the invention, one deck or multilayer is applied according to the step of radiation-hardenable composition of the present invention, preferably after the step applying priming paint, and preferably before the step of applicator surface coating.Typically, one or more sand milling (sanding) step is also comprised to improve the performance such as adhered to according to method of the present invention.Find sand milling and/or owe solidification (undercuring) to improve inter coat adhesivity.
The priming paint that can apply typically has about 5-10g/m 2coating wt.Before using prime coat, preferably by base material sand milling slightly.
Seal coating is recoat layer typically, and general weight is at least 10g/m 2.For parquet floor coating, may expect that total seal coating weight is 60-75g/m 2.
These recoat layers are difficult to a step and apply.In addition, will be better if apply several coating machine performance.Typically apply three to four-layer seal layer, every layer of about 25-10g/m 2.Mostly just solidify the seal coating of the first layer and final layer completely to improve sanding property (sandability) (such as using 2 medium pressure mercury lamp H-bulb 120w/cm 18m/min).Other seal coating owes solidification or gel typically via being exposed to such as low UV source (such as using medium pressure mercury lamp H bulb 120w/cm-18m/min).
In order to obtain good outward appearance, glossiness and resistance to soiling, usually applying and applicator surface coating after solidifying one or more layers seal coating.Preferably sand milling base material (such as mechanical system) before applicator surface coating on the base material through coating.Typically, the weight of top coat is 8-20g/m 2.Top coat can be 8-10g/m as weight 2single layer apply.Or top coat can be made up of 2 different layers, and the first layer typically has 10g/m 2weight, be 5g/m applying weight 2the second layer before make described the first layer gel or owe solidification, then solidify completely.
Can be coated with by standard rollers and apply different coating and coating.
The invention still further relates to the method for the goods of preparation coating, comprise the step with radiation-hardenable composition coated article of the present invention.Another aspect of the present invention relates to partly or completely with the goods that radiation-hardenable composition of the present invention applies.
The present invention is explained explanation by following nonlimiting examples.
Embodiment 1:
By the polypropylene glycol (30000mPa.s initial by hydroxyethyl acrylate, tolylene diisocyanate and triol of 60kg , MW=2000g/mol) the propylene glycol diacrylate of the aromatic urethanes triacrylate (oligopolymer 1) be obtained by reacting and 20kg, 20kg tripropylene glycol diacrylate and 1kg monoethanolamine mix.React and carry out, until reach residual amine content lower than 500ppm being no more than at the temperature of 90 DEG C.The feature of the resin obtained is listed in table 1.
Embodiment 2:
The resin of embodiment 2 is obtained according to the identical method described in embodiment 1.Composition and content is as shown in table 1 regulates.The feature of the resin obtained also is listed in table 1.
Embodiment 3:
Obtain the resin of embodiment 3 according to the identical method described in embodiment 1, but use by the initial polypropylene glycol (3900mPa.s of hydroxyethyl acrylate, tolylene diisocyanate and glycol , MW=1500g/mol) and the aromatic urethanes diacrylate (oligopolymer 2) that is obtained by reacting.Composition and content is as shown in table 1 regulates.The feature of the resin obtained also is listed in table 1.
Embodiment 4:
The resin of embodiment 4 is obtained according to the identical method described in embodiment 3.But, when reaching residual amine content lower than 1000ppm, add the second diluting monomer of specified amount and whole mixing until obtain homogeneous medium.Composition and content is as shown in table 1 regulates.The feature of the resin obtained also is listed in table 1.
Embodiment 5:
Before adding amine, the aromatic urethanes diacrylate (oligopolymer 2) be obtained by reacting by the polypropylene glycol initial by hydroxyethyl acrylate, tolylene diisocyanate and glycol of 234.5kg mixes with the propylene glycol diacrylate of 40kg.When reaching residual amine content lower than 500ppm, add the second diluting monomer of 15kg propylene glycol diacrylate and specified amount, and whole mixing is until obtain homogeneous medium.Composition and content is as shown in table 1 regulates.The feature of the resin obtained also is listed in table 1.
Embodiment 6:
Obtain the resin of embodiment 6 according to the identical method described in embodiment 4, but use by the initial polypropylene glycol (3080mPa.s of hydroxyethyl acrylate, isophorone diisocyanate and glycol , MW=1200g/mol) and the aliphatic carbamate diacrylate (oligopolymer 3) that is obtained by reacting and use propoxylated glycerol triacrylate.Composition and content is as shown in table 1 regulates.The feature of the resin obtained also is listed in table 1.
Embodiment 7:
Obtain the resin of embodiment 7 according to the identical method described in embodiment 4, but use aliphatie diamine N, N '-dual-tert-butyl ethane diamine (DTBEDA) replaces monoethanolamine.Composition and content is as shown in table 1 regulates.The feature of the resin obtained also is listed in table 1.
Embodiment 8 to 14 and 15R:
Assign to prepare the curable sealing preparaton of UV by the one-tenth mixed as described in table 2 at 25 DEG C.Then evaluate the reactivity of preparaton, the results are shown in Table 2.Number is weight part.
Embodiment 16 to 22 and 23R:
Sealing ply is prepared according to following scheme.
By 15g/m 2the UV curable priming paint preparaton paint of wet embodiment 24 is on the beech wood of sand milling (150/180 aluminum oxide sandpaper) slightly.The mercury UV lamp of priming paint 120W/cm solidifies with 18m/min.
Then, according to table 3, use roller coating machine to apply the curable sealing preparaton of UV that threeply degree is the table 2 of 20-22 μm step by step.First and the third layer mercury UV lamp of two 120W/cm solidify with 18m/min, and slightly use hand sand milling.The second layer mercury UV lamp of a 120W/cm solidifies with 18m/min, and not sand milling.
Finally, apply the top coat preparaton that the UV of 8 μm of thick embodiments 25 is curable, and solidify completely with 5m/min with the lamp of 2 80W/cm.
Evaluate adhesivity, the Hamberger of the beech wood sample of coating grits wear (grit feeder), cold shortness (cold-check) and yellow.Obtain that the results are shown in Table 3.
Embodiment 24:
By preparing the curable priming paint preparaton of UV 25 DEG C of mixing following ingredients.Number is weight part:
100 parts 6558
10 parts 12
1.5 part bCPK(is purchased from the light trigger of Cy t ec)
Embodiment 25:
By preparing the preparaton of the curable top coat of UV 25 DEG C of mixing following ingredients.Number is weight part:
30 parts 265
10 parts 810
42 parts of DPGDA
3 parts bP(is purchased from the light trigger of Cytec)
2 parts hDMAP(is purchased from the light trigger of Cytec)
8 parts 162C(is from the matting agent of Grace)
2 parts of Lancowax PP 1362(are from the Poly Propylene Wax of Langer & Co)
1 part of DOW CORNING PA-11(is from the flowing additive of Dow Corning)
2 parts tS 100(is from the matting agent of Evonik)
HDMAP=2-hydroxy-2-methyl-1-phenyl-acetone
Running through whole invention and embodiment uses following methods evaluation according to the character of amino of the present invention (methyl) acrylate and radiation-hardenable composition:
Amine content: amine content measures by making the quantitative reaction of primary amine and tertiary amine and CS2.The thiocarbamate obtained adopts NaOH to carry out titration with potentiometric measurement.Amine content value ppm represents.
Cone & Plate viscosity: according to DIN EN ISO 3219, at 25 DEG C with the shearing rate 20s-1 rotary viscosity measuring viscosity of regulation.Viscosity number mPa.s represents.
Reactive: by the film paint of 25 μm white nonabsorbable paper, and under being exposed to from 80W/cm non-focusing medium pressure mercury lamp UV radiation with the line speed of regulation.Change line speed to measure the maximum line speed in order to obtain complete cured film.The complete curing characteristics of film is by being put in surface and then repeatedly rubbing and assessment with cotton yarn with finger by some talcums.As long as observe matt form, then film does not solidify completely, and must reduce line speed.Coating can also through benefiting from 50 round trip frictions of the cotton pad be immersed in acetone.Completely crued film is not visually by the impact of this test.Need the reactivity being called coating by the UV-dosage (represent by line speed (m/min), adopt the lamp power (W/m) determined) of these two tests.
Adhesivity: by the film paint priming paint of 20-22 μm and according in reactive methods/approaches describe ground solidify completely.In coating, square pattern is carved with cutting knife.One row adhesive tape (Tesa 4104) is pressed on the surface, and gets rid of the gas in middle layer.Then adhesive tape is removed rapidly.Based on the square number removed by adhesive tape, provide adhesivity value: the square removing of 0B(100%), the square removing of 1B(65-35%), the square removing of 2B(35-15%), the square removing of 3B(15-5%), 4B(lower than 5% square removing), 5B(0%).
Hamberger- (coin test): coating system paint completely, on the beech of sand milling, is solidified and is placed in Hamberger- on tester.This device has the screw rod that can rotate and change the pressure of the coin in coating.Pressure progressively increases until cause the scratch of several centimetres on the surface of coating.Applied pressure is higher, then scrath resistance is better.Newton represents scrath resistance.
Grits wear (Grit feeder): the method based on standard method of test ASTMF510-93, and uses the taber abrader 5150 with the wheel (S-39) of leather covered; The gravel used in this test is the Alodur ESK 240EN14354 type from Treibacher.Coating system to be completely applied on the beech of sand milling and to solidify.Before test, all equipment and base material are regulated at least 24 hours in surge chamber (21 ± 1 DEG C, relative humidity 50 ± 5%).Carried out wearing away until there is spot by the base material of coating in the step of 500 circulations, its floating coat is removed (point of beginning) completely.After applying methylene blue solution, when forming blue spot on sample, reach point of beginning.After determining point of beginning, carry out the abrasion of another 500 circulation.Apply methylene blue again easily for visual comparison.Abrasion are measured by weight loss (mg, tolerance range ± 0.1mg) after each 500 circulation steps.
Cold shortness: coating system paint is completely solidified on the beech of sand milling.Make the base material of coating to stand at-20 DEG C 1 hour and 2 × 25 circulations of 1 hour at+70 DEG C.When still not having crack, coating is by test.
Yellow: by the film paint of 25 μm white nonabsorbable paper, solidification is also exposed to the UV light of Ultra-Vialux 300W lamp in complete totally enclosed drum.Distance between lamp and sample is 50cm.With Supercolor type measurement device yellow (δ b) after exposure 96 hours, and contrast with initial stage yellowing (before exposure).
By gpc measurement weight-average molecular weight and number-average molecular weight: number-average molecular weight (Mn), weight-average molecular weight (Mw) and polymolecularity measure typically via the gel permeation chromatography (GPC) of routine, adopt the polystyrene standards EasyCal(molecular weight ranges from Polymer Laboratories: 200-400.000g/mol).By the sample dissolution of small portion in tetrahydrofuran (THF) (THF), and inject the liquid chromatograph (Merck-HitachiL7100) being equipped with 3 PLGel Mixed-D LS polystyrene divinylbenzene GPC post (300mm × 7.5mm × 5 μm).Based on its molecular size in the solution, GPC post is by the Component seperation of sample and detected by refractive index detector.Collected and processing data by Polymer Laboratories Cirrus GPC software.
Table 1: the constituent and properties of resin
Oligopolymer 1: by the aromatic urethanes triacrylate be obtained by reacting of the initial polypropylene glycol of hydroxyethyl acrylate, tolylene diisocyanate and triol.
Oligopolymer 2: by the aromatic urethanes diacrylate be obtained by reacting of the initial polypropylene glycol of hydroxyethyl acrylate, tolylene diisocyanate and glycol.
Oligopolymer 3: by the aliphatic carbamate diacrylate be obtained by reacting of the initial polypropylene glycol of hydroxyethyl acrylate, isophorone diisocyanate and glycol.
DPGDA: propylene glycol diacrylate
TPGDA: tripropylene glycol diacrylate
OTA480: propenoxylated glycerol tri-acrylate
EPEA: the phenoxyethyl acrylate of ethoxylation;
MEA: monoethanolamine
DTBEDA:N, N '-dual-tert-butyl ethane diamine
Table 2: sealing ply formula
Table 3: sample evaluation
Result display in table 2 and 3, combines the reactivity and excellent adhesivity, scrath resistance and rub that improve according to amino of the present invention (methyl) acrylate.Amino of the present invention (methyl) acrylate allows the coating of the rub obtaining having raising further.Find that the yellow of amino of the present invention (methyl) acrylate is slightly better than the such as comparative example 23R of the resin based on non-amination.

Claims (13)

1. amino (methyl) acrylate, it is obtained by least one amine A and the mixture reaction of thinner C of at least one (methyl) acroleic acid esterification of at least one carbamate (methyl) acrylate B and 1-85wt% comprising 15-99wt%
Wherein said amine A is selected from and comprises at least one primary amino-NH 2primary amine A1 and/or be selected from the secondary amine A2 comprising at least two secondary amino group-NH,
Wherein amine A consumption for the equivalence ratio of (methyl) acrylic acid series double bond amino-N-H that provided by amine A is provided provides with the thinner C by carbamate (methyl) acrylate B and (methyl) acroleic acid esterification be 0.1 to 0.9
Wherein said carbamate (methyl) acrylate B comprises 2 to 4 (methyl) acrylate-functional groups,
The thinner C of wherein said (methyl) acroleic acid esterification is selected from three (methyl) acrylate, two (methyl) acrylate and/or single (methyl) acrylate.
2. amino according to claim 1 (methyl) acrylate, wherein said amine A1 corresponds to formula R 1-NH 2, wherein R 1for alkyl, it is optionally replaced by hydroxyl, alkoxyl group, tertiary amine and/or aryl.
3. amino according to claim 1 and 2 (methyl) acrylate, wherein said carbamate (methyl) acrylate B is carbamate two (methyl) acrylate.
4., according to amino (methyl) acrylate of claim 1 or 2, the elongation at break of wherein said carbamate (methyl) acrylate B is 10-500%.
5. amino according to claim 1 and 2 (methyl) acrylate, the thinner C of wherein said (methyl) acroleic acid esterification is two (methyl) acrylate.
6. the coating composition of radiation-hardenable, it comprises the amino of at least one as described in any one of claim 1 to 5 (methyl) acrylate of 5wt%-99wt%.
7. composition according to claim 6, it comprises the thinner D of at least one (methyl) acroleic acid esterification further.
8. composition according to claim 7, the thinner D of wherein said (methyl) acroleic acid esterification is selected from two (methyl) acrylate and/or single (methyl) acrylate.
9. the composition according to claim 7 or 8, the thinner D of wherein said (methyl) acroleic acid esterification is single (methyl) acrylate.
10. the purposes of amino (methyl) acrylate in the composition being applicable to the radiation-hardenable preparing coating, tackiness agent, ink or varnish as described in claim 1 to 5 any one.
11. for applying the method on floor, and described method comprises: on floor base material, apply one deck or multilayer according to the composition of the radiation-hardenable of any one of claim 6 to 9, and by being exposed to radiation by the described composition solidification applied.
12. methods according to claim 11, wherein said floor is timber floor.
13. methods according to claim 11 or 12, wherein apply one deck or multilayer according to the step of the composition of any one of claim 6 to 9 after the step applying prime coat, and before the step of applicator surface coating.
CN201180008220.3A 2010-04-19 2011-04-11 Amino (methyl) acrylate of radiation-hardenable Active CN102741221B (en)

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PCT/EP2011/055604 WO2011131501A1 (en) 2010-04-19 2011-04-11 Radiation curable amino(meth)acrylates

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2769238A1 (en) * 2009-07-28 2011-02-03 Photokinetic Coatings & Adhesives, Llc. Uv-curable floor sealants
EP2583986A1 (en) * 2011-10-17 2013-04-24 Cytec Surface Specialties, S.A. Fluorinated water-oil repellency agents
FR3022544B1 (en) 2014-06-23 2018-01-05 Arkema France MULTIFUNCTIONAL ACRYLIC OLIGOMERS OF BRANCHED STRUCTURE, BY POLYADDITION BETWEEN AMINES AND MULTIFUNCTIONAL ACRYLATES.
EP3294815B1 (en) * 2015-05-15 2020-09-02 Sun Chemical Corporation Energy curable inkjet inks and coating compositions
US10400127B2 (en) * 2015-06-30 2019-09-03 Pressing Developments, L.L.C. Methods of preparing porous wood products for painting and finishing
CA3028371A1 (en) * 2015-06-30 2017-01-05 Widner Product Finishing, Inc. Sealing and finishing porous panel products and methods of production
EP3401370A1 (en) * 2017-05-10 2018-11-14 Allnex Belgium S.A. Amino (meth)acrylates
PL3929256T3 (en) * 2020-06-22 2024-06-17 Allnex Belgium, S.A. Polymeric amino (meth)acrylate
CN114213622B (en) * 2021-12-21 2023-05-16 江苏三木化工股份有限公司 Preparation method of modified polyurethane acrylic ester photo-curing resin
KR102519042B1 (en) * 2022-09-28 2023-04-05 권은진 Manufacturing method of high-viscosity adhesive with improved dispersion stability

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844916A (en) * 1972-09-18 1974-10-29 Desoto Inc Radiation curable non-gelled michael addition reaction products
WO2002032851A1 (en) * 2000-10-20 2002-04-25 Ucb, S.A. Dimethylamine/ester adducts and their use in polymerizable compositions
CN101193926A (en) * 2005-06-10 2008-06-04 氰特表面技术有限公司 Low extractable radiation curable compositions containing aminoacrylates
CN101479233A (en) * 2006-06-29 2009-07-08 氰特表面技术有限公司 Radiation curable amino(meth)acrylates

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4045416A (en) † 1971-01-21 1977-08-30 Union Carbide Corporation Amine acrylate addition reaction product compositions
US5792827A (en) † 1994-01-13 1998-08-11 Basf Lacke + Farben, Ag Addition products, radiation-curable surface coating compositions based on the addition products and their use for woodcoating and papercoating
EP0731121A3 (en) † 1995-03-09 1997-06-11 Basf Ag Aminomodified urethane-acrylates
US5648173A (en) * 1996-01-25 1997-07-15 Dow Corning Corporation Room temperature, moisture-curable abrasion-resistant coating composition having enhancable weatherability
JP2002060442A (en) 2000-08-18 2002-02-26 Nippon Synthetic Chem Ind Co Ltd:The Ultraviolet-curing resin composition and its use
GB0022188D0 (en) 2000-09-11 2000-10-25 Interactive Comm Services Ltd Voice-over internet protocol
JP2004196864A (en) * 2002-12-16 2004-07-15 Toyo Ink Mfg Co Ltd Method for producing polyurethane resin and printing ink using the same
AU2005312088B2 (en) * 2004-11-30 2012-07-12 Syngenta Participations Ag Process and composition for coating propagation material
US7968198B2 (en) * 2005-08-25 2011-06-28 Ppg Industries Ohio, Inc. Polyurea coating comprising a polyamine/mono(meth)acrylate reaction product

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844916A (en) * 1972-09-18 1974-10-29 Desoto Inc Radiation curable non-gelled michael addition reaction products
WO2002032851A1 (en) * 2000-10-20 2002-04-25 Ucb, S.A. Dimethylamine/ester adducts and their use in polymerizable compositions
CN101193926A (en) * 2005-06-10 2008-06-04 氰特表面技术有限公司 Low extractable radiation curable compositions containing aminoacrylates
CN101479233A (en) * 2006-06-29 2009-07-08 氰特表面技术有限公司 Radiation curable amino(meth)acrylates

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US20120308734A1 (en) 2012-12-06
TWI541219B (en) 2016-07-11
CN102741221A (en) 2012-10-17
EP2383254A1 (en) 2011-11-02
US9272989B2 (en) 2016-03-01
WO2011131501A1 (en) 2011-10-27
TW201141815A (en) 2011-12-01
EP2560948A1 (en) 2013-02-27
KR20130061674A (en) 2013-06-11

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